TWI467068B - Polyurethane elastic yarn and method for production thereof - Google Patents

Description

Polyurethane elastic yarn and manufacturing method thereof

The present invention relates to a polyurethane elastic yarn having high heat resistance at the time of dyeing (especially, high heat resistance when unsaturated fatty acid or heavy metal is attached), high elastic recovery property, high tensile strength, and the like Production method.

The elastic fiber is widely used in stretchable clothing applications or industrial materials for socks, underwear, sportswear, and the like because of its superior stretch characteristics.

For the polyurethane elastic yarn which is widely used as such an elastic fiber, high tensile strength, high elastic resilience, high heat resistance, and thermosetting property are required. Among them, high heat resistance is expected to be used in the form of a mixed fabric combined with a polyester yarn, and in particular, heat resistance at the time of dyeing processing is very important.

That is, in the case of being used in combination with a polyester yarn or in the case of rendering an intermediate color, the dyeing temperature itself tends to increase during the dyeing process. In addition, in order to obtain good stretchability, dimensional stability, and surface quality, the dry heat treatment is performed at a high temperature before dyeing. Therefore, the elastic yarn must have high heat resistance.

In addition, the elastic yarn is attached to the yarn finish oil imparted in the course of its manufacture. Further, in the hybrid elastic fabric, the oil agent is transferred from the mixed yarn of the polyester yarn or the like to the elastic yarn, so that the adhesion of the lubricating oil to the elastic yarn is inevitable. And, it is attached in the weaving process. The mechanical oil on the weaving machine will transfer and adhere to the elastic yarn. However, the original yarn oil agent in the polyester yarn or the nylon yarn generally uses an unsaturated fatty acid. On the other hand, an elastic yarn containing a thermal embrittlement promoting substance of an unsaturated fatty acid is applied to an elastic yarn which is used in combination with the polyester yarn or the nylon yarn to form a mixed elastic fabric. Further, although the oil agent is in a small amount, it is also incorporated into a mechanical metal component or the like. When a hot embrittlement promoting substance or a trace amount of a metal component of an unsaturated fatty acid is present in an oil agent attached to an elastic yarn, the deterioration of the polyurethane elastic yarn is promoted due to the interaction thereof, causing yarn breakage or Local strength is reduced. Further, depending on the situation, there is a possibility that the fine perforation of the fabric may cause a problem that is unexpectedly large.

Therefore, it is strongly required to have superior heat resistance even in the state where an unsaturated fatty acid or a metal component is attached to the elastic yarn at the same time as the oil agent. Further, although it is contrary to the high heat resistance, it is required to be heat-set as much as possible at a lower temperature than before, as it is in the past.

However, when the polyurethane elastic yarn containing a benzotriazole-based ultraviolet absorber for improving light embrittlement resistance is treated with copper-containing water, there is a problem that yellowing is likely to occur. In order to prevent the yellowing, there has been proposed a technique in which a metal inerting agent is contained in an elastic yarn so that the complex compound is not generated between the benzotriazole-based ultraviolet absorber and copper (see Patent Document 1). ). However, this technique further contains a metal inert agent to prevent the photo-brittleness and further contains a metal inert agent in a polyurethane yarn containing a necessary amount of a benzotriazole-based ultraviolet absorber to prevent a benzotriazole system. Ultraviolet absorption The yellowing caused by the charging agent and copper, but even if a metal inert agent is added, it is difficult to improve the heat resistance of the polyurethane elastic yarn during dry heat treatment or high temperature dyeing. For example, in the case of dry heat treatment at a high temperature before dyeing, or in the case of dyeing at a high temperature with a mixed fabric of polyester yarn, the heat resistance is still unsatisfactory, and there are restrictions on use. .

Moreover, there has been proposed a kind of trinitrogen to protect the fading due to atmospheric smoke and light. (Triazine) A technique of a light absorbing agent and a urethane elastic yarn of an N,N-dialkyl semicarbazide group (see Patent Document 2). However, this technique is a kind of polyurethane elastic yarn containing a necessary amount of light absorbing agent for reducing the fading caused by atmospheric smoke and light, and further introducing a semi-carboxy group to prevent fading, and therefore, excessive The measure of adding a light absorbing agent tends to hinder heat resistance during dry heat treatment of the polyurethane elastic yarn or high temperature dyeing. Therefore, the heat resistance is still unsatisfactory and the use is limited in the case of dry heat treatment at a high temperature before dyeing or in the case of dyeing at a high temperature with a mixed fabric of polyester yarn. The situation.

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2000-169700 (Invention Patent Document 2) Invention Patent No. 3028237

The present invention is to solve the problems of the prior art as described above, and to provide A polyurethane elastic yarn which exhibits excellent heat resistance even when an unsaturated fatty acid or a heavy metal adheres to a yarn even at a high temperature dyeing, and which has high elastic recovery property and high elongation, and a method for producing the same.

For the purpose as described above, the polyurethane elastic yarn of the present invention employs the following measures.

That is, it is characterized in that it is an elastic yarn composed of a polymer diol having a main constituent component of a polymer diol and a diisocyanate, and contains (a) a sterically hindered phenol compound, (b) N, N. The content of the dialkylcarbazone compound and the (c) nitrogen-containing aromatic compound is 0.01% by weight or more and 0.30% by weight or less.

Further, the method for producing a polyurethane elastic yarn of the present invention is characterized in that (a) a hindered phenol is added to a solution in which a main component is a polymer diol and a polyurethane of a diisocyanate. a compound, (b) an N,N-dialkylhalocyanine compound, and (c) a nitrogen-containing aromatic compound, and a ratio of (b) a nitrogen-containing aromatic compound to a polyurethane-based compound Spinning is carried out after a polyurethane spinning solution of 0.01% by weight or more and 0.30% by weight or less.

The polyurethane elastic yarn according to the present invention exhibits superior heat resistance (especially heat aging resistance) even when unsaturated fatty acid or heavy metal adheres to the yarn at high temperature dyeing, and has high The elastic resilience, high tensile strength, etc., by using the clothes made of the elastic yarn, etc., will have excellent peelability, wearability, wearing feeling, and dyeing. Color rendering, discoloration resistance, appearance quality, etc.

[Best Embodiment of the Invention]

Hereinafter, the present invention will be described in more detail.

First, a polyurethane of a matrix polymer constituting the polyurethane elastic yarn of the present invention will be described.

The polyurethane to be used in the present invention is not particularly limited as long as it is a polymer diol and a polyisocyanate of a diisocyanate. In addition, there are no special restrictions on the synthesis method.

That is, for example, it may be a polyurethane-urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine, or may be a polymer diol, a diisocyanate, or a low molecular weight diol. A polyurethane formed. Further, a polyurethane-urea which uses a compound having a hydroxyl group and an amine group in a molecule as a segment growth agent may also be used. Further, a polyfunctional diol or an isocyanate or the like having a trifunctional or higher functionality may be used in combination without inhibiting the efficacy of the present invention.

Representative structural units for constituting the polyurethane used in the present invention are explained below.

The polymer diol used for the structural unit constituting the polyurethane is preferably a polyether diol, a polyester diol, a polycarbonate diol or the like. Further, from the viewpoint of imparting flexibility and elongation to the elastic yarn in particular, it is preferred to use a polyether diol.

The polyether diol preferably comprises a copolymerized diol compound having a unit represented by the following general formula (I): (However, a, c are integers from 1 to 3, b is an integer from 0 to 3, and R1, R2 are H or an alkyl group having 1 to 3 carbon atoms).

The "polyether diol compound" specifically includes polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, and polytetramethylene ether glycol ( In the following, abbreviated as "PTMG", tetrahydrofuran (hereinafter, abbreviated as "THF") and 3-methyl-THF copolymer modified PTMG, THF and 2,3-dimethyl-THF The polymer is modified with PTMG, a modified PTFE of THF and neopentyl glycol, a random copolymer of THF and ethylene oxide and/or propylene oxide, and the like. One type of these polyether diols may be used, or two or more types may be used in combination or copolymerized. Among them, PTMG or modified PTMG is preferred.

Further, from the viewpoint of improving the abrasion resistance and light resistance of the polyurethane yarn, it is preferred to use butylene adipate, polycaprolactone diol, and 3-methyl-1. a polyester diol having a side chain of a polyester diol obtained by a polycondensation reaction of a mixture of 5-pentanediol and a poly(extension propylene polyol) with adipic acid or the like, or containing 3,8 a polycarbonate diol comprising a dicarboxylic acid component composed of dimethyl sebacic acid and/or 3,7-dimethyl sebacic acid and a dicarboxylic acid ester unit derived from a diol component.

Further, these polymer diols may be used singly or in combination of two or more kinds or copolymerized.

The molecular weight of these high molecular weight diols is preferably from 1,000 to 8,000, preferably from 1,000 to 8,000, in terms of number average molecular weight, in order to achieve the desired level of elongation, strength, heat resistance, etc. when the elastic yarn is made into an elastic yarn. It is 1,800 to 6,000. By using a polymer diol having a molecular weight in this range, an elastic yarn having excellent elongation, strength, elastic restoring power, and heat resistance can be obtained.

Next, the diisocyanate used to constitute the structural unit of the polyurethane, particularly from the viewpoint of synthesizing a polyurethane having high heat resistance or strength, is preferably a diphenylmethane diisocyanate. (hereinafter, simply referred to as "MDI"), "aromatic diisocyanate" such as tolyl diisocyanate, benzene 1,4-diisocyanate, benzodimethyl diisocyanate or 2,6-naphthalene diisocyanate. Further, the "alicyclic diisocyanate" is preferably, for example, methylene-bis(4-cyclohexyl isocyanate) (hereinafter, abbreviated as "PICM"), isophorone diisocyanate, methylcyclohexane- 2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrobenzodimethylisocyanate, hexahydro-tolyl diisocyanate, octahydrogen -1,5-naphthalene diisocyanate or the like. The "aliphatic diisocyanate" is effective for particularly suppressing the yellowing of the polyurethane elastic yarn. Further, these diisocyanates may be used singly or in combination of two or more.

Next, it is preferred to use at least one of a low molecular weight diamine and a low molecular weight diol for the segment growth agent constituting the structural unit of the polyurethane. In addition, it may also be, for example, ethanolamine having a hydroxyl group and an amine in the molecule. Base.

The molecular weight of the low molecular weight diamine and the low molecular weight diol is preferably from 30 to 300, and more preferably from 40 to 200 from the viewpoint of obtaining a high melting point polyurethane.

Preferred "low molecular weight diamines" include, for example, hydrazine, hydrazine, ethylenediamine, 1,2-propylenediamine, 1,3-propanediamine, hexamethylenediamine, P-phenylenediamine, p-xylylenediamine, m-phenylenediamine, p-, p-methylenediphenylamine, 1,3-cyclohexyldiamine, hexahydromethyl Phenyldiamine, 2-methylpentamethylenediamine, bis(4-aminophenyl)phosphine oxide, and the like. It is preferred to use one or two or more kinds from among them, and particularly preferably ethylenediamine. By using ethylenediamine, a yarn having superior elongation, elastic recovery, and heat resistance can be obtained. To the extent that the effect of the present invention is not lost, a triamine compound which forms a crosslinked structure such as diethylenetriamine or the like may be added to such a chain extender.

In addition, representative of "low molecular weight diol" includes: ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate , 1-methyl-1,2-ethanediol, and the like. It is preferred to use one or two or more kinds from these. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. When such a product is used, a diol-extended polyurethane can produce a yarn having high heat resistance and high strength.

Further, the molecular weight of the polyurethane used to constitute the polyurethane elastic yarn of the present invention is preferably a number average molecular weight from the viewpoint of obtaining durability or high strength fibers. 40,000 or more and 150,000 or less. In addition, the molecular weight is determined by GPC. And the value calculated in terms of polystyrene.

Further, the polyurethane used to constitute the elastic yarn of the present invention is particularly preferable from the viewpoint of obtaining a problem of practical application including no process passability and having superior high heat resistance. In view of the above, the polymer diol and the diisocyanate are used, and the melting point on the high temperature side is in the range of 200 ° C or more and 300 ° C or less. Here, the "melting point on the high temperature side" corresponds to the so-called "hard segmental crystallization" of polyurethane or polyurethane-urea when measured by DSC (differential scanning calorimeter). Melting point".

That is, by using PTMG having a molecular weight of 1,000 or more and 6,000 or less as a polymer diol, MDI is used as a diisocyanate selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, and ethylene-2. a polyurethane obtained by polymerizing at least one of a group consisting of an amine, 1,2-propylenediamine, and 1,3-propanediamine as a segment growth agent, and having a melting point of 200 at a high temperature side Elastic yarns made of polyurethanes in the range of °C or more and 300 °C or less are particularly excellent in elongation, do not include problems in practical application of process passability, and have excellent heat resistance. Therefore, it is better.

Further, in order to achieve a melting point of the high temperature side of the polyurethane yarn of 200 ° C or more and 300 ° C or less, it is preferred to select a ratio of the diisocyanate to the polymer diol and the segment growth agent by a preliminary test. The method of optimal value. These polyurethanes are suitable for use as the polyurethane used in the present invention.

The polyurethane elastic yarn of the present invention uses the above-mentioned polyurethane as a matrix polymer and contains (a) a sterically hindered phenol compound. And (b) a nitrogen-containing aromatic compound, and (c) a nitrogen-containing aromatic compound is contained in an amount of 0.01% by weight or more and 0.30% by weight or less.

(a) a sterically hindered phenol-based compound (hereinafter, simply referred to as "(a) compound"), (b) an N,N-dialkylsemicarbazone compound (hereinafter, simply referred to as "(b) compound") And (c) a nitrogen-containing aromatic compound (hereinafter, simply referred to as "(c) compound") is not only improved in general heat aging resistance by capturing the antioxidant effect of a radical, etc., or by absorbing specific ultraviolet rays. It is generally effective in light resistance, and can capture unsaturated fatty acids and metal components to make them harmless, thereby improving the deterioration resistance of the polyurethane elastic yarns.

Specifically, the (a) compound, the (b) compound, and the (c) compound act mainly in the manner of synergistic metal capture, and the (a) compound and the (b) compound synergistically capture unsaturated fatty acids. The way to make a difference. Therefore, by using these compounds in combination, even if the polyurethane elastic yarn to which an unsaturated fatty acid or a heavy metal is attached is dyed at a high temperature, superior heat resistance can be exerted, and the present invention is intended to exhibit the desired heat. efficacy. Further, when the content of the compound (c) (ratio to the yarn) is 0.01% by weight or more and 0.30% by weight or less, the effect can be enhanced by the synergistic effect with the compound (a) and the compound (b). It improves the antioxidant effect and fully captures the trace amount (less than 100 ppm) of heavy metals mixed in the dyeing to make it harmless. Here, the content of the compound (c) (the ratio with respect to the yarn) is 0.01% by weight or more and 0.30% by weight or less, and generally corresponds to an aromatic ring nitrogen atom system of 5 per 1 kg of yarn. The case exists in the range of 200 milliequivalents (meq/kg).

On the other hand, since the aromatic ring system containing a nitrogen atom is likely to be thermally decomposed, and when the content of the compound (c) is large (that is, when the aromatic ring nitrogen atom is more than 200 milliequivalents), the ratio (a) The synergistic effect of the compound and the compound (b), the radical generation due to thermal decomposition will predominate, the heat resistance is lowered, or the ruthenium structure is formed to cause thermal discoloration, and therefore, high heat resistance at the time of dyeing cannot be obtained. The function. Further, although the compound (c) may be used as a light stabilizer to contain a large amount, if the content is as large as more than 0.30% by weight, the dyeing time is not obtained as the object of the present invention. Heat resistance and other effects. Based on the above viewpoints, it is preferred that the content of the compound (c) is an appropriate amount which is not excessive. Specifically, a preferred range is from 0.01 to 0.25% by weight, more preferably from 0.05 to 0.20% by weight, most preferably from 0.07 to 1.80% by weight.

Further, even if either of the (a) compound and the (b) compound is absent, the capture efficiency against unsaturated fatty acids and metal resistance is still unsatisfactory. Further, although the content of these is preferably contained to a certain extent in order to obtain the effect of the present invention, if the amount is excessively increased, the inherent properties of the polyurethane elastic yarn are easily impaired, and therefore, a) The content of the compound is preferably 0.1% by weight or more and 6.0% by weight or less, and the content of the compound (b) is preferably 1.0% by weight or more and 6.0% by weight or less.

As described above, in the present invention, it is necessary to contain (a) a hindered phenol compound, (b) an N,N-dialkylhalocyanine compound, and (c) A nitrogen-containing aromatic compound.

The "(a) compound" used in the present invention, that is, the "hindered phenolic compound" includes a phenolic compound which is generally known as an antioxidant. For example, 3,5-di-tris-butyl-4-hydroxy-toluene, n-octadecyl-β-(4'-hydroxy-3',5'-di-tertiary-butylphenyl Propionate, hydrazine [methylene-3-(3',5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl -2,4,6'-parade (3,5-di-tris-butyl-4-hydroxybenzyl)benzene, calcium (3,5-di-tertiary-butyl-4-hydroxy-benzene Methyl-ethyl-phosphate), triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-double 1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl]2,4,8,10-tetra Oxyspiro[5,5]undecane, tocopherol, 2,2'-ethylenebis(4,6-di-tertiary-butylphenol), N,N'-bis[3- (3,5-di-tris-butyl-4-hydroxyphenyl)propanyl]anthracene, 2,2'-oxalylamine bis[ethyl-3-(3,5-di-tris- Butyl-4-hydroxyphenyl)propionate], 1,1,3-glycol(2-methyl-4-hydroxy-5-tertiary-butylphenyl)butane, Ethyl-1,2-bis(3,3-bis[3-tert-butyl-4-hydroxyphenyl]butyrate), ethylidene-1,2-bis(3-[3-three Grade-butyl-4-hydroxyphenyl]butyrate), 1,1-bis(2-methyl-5-tris-butyl-4-hydroxyphenyl)butane, 1,1,3- ((2-methyl-5-tertiary-butyl-4-hydroxyphenyl)butane, 1,3,5-paran (3',5'-di-tertiary-butyl-4'-hydroxyl Benzyl)-S-trinitrogen -2,4,6(1H,3H,5H)-trione, 1,3,5-gin (3'-tertiary-butyl-4'-hydroxy-5-methylbenzyl)-S- Trinitrogen -2,4,6(1H,3H,5H)-trione, 1,3,5-gin (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1 , 3,5-trinitrogen -2,4,6(1H,3H,5H)-trione, and the antioxidant for the polyurethane elastic yarn is also suitably used for the well-known high molecular weight sterically hindered phenolic compound.

Preferred specific examples of such high molecular weight sterically hindered phenolic compounds are the use of an addition polymer of divinylbenzene and cresol, an addition polymer of dicyclopentadiene and cresol, an isobutylene adduct, A polymer of a compound of chloromethylstyrene and cresol, ethylphenol, tert-butylphenol or the like. Among them, divinylbenzene and chloromethylstyrene may be para- or meta-. Further, cresol, ethylphenol, and tertiary butylphenol may be either ortho-, meta-, or para-.

Among them, from the viewpoint of stabilizing the viscosity of the raw material spinning solution of the polyurethane yarn, suppressing the amount of volatilization in the spinning, and obtaining good spinnability, the molecular weight is preferably 300 or more. For the purpose of effectively exhibiting high spinning speed, heat resistance during dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, it is preferred to use 1,3,5-para (4-three Grade-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), an adduct of divinylbenzene and p-cresol, and Any of the polymers having a repeat number of 6 to 12 or used in combination. Among them, particularly preferred is 1,3,5-gin (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione. In addition, if (a) compound and (c) compound select trinitrogen In the case of a compound, a particularly high synergistic effect can be obtained in terms of heat resistance at the time of dyeing. Among them, it is particularly preferred that the compound (a) is 1,3,5-gin(4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three nitrogen -2,4,6(1H,3H,5H)-trione, and the compound (c) is 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-triazole .

The "(b) compound" used in the present invention is other than the compound having an N,N-dialkylcarbazone compound in the molecule and having N,N-dialkylcarbazone in the molecule. Special restrictions. For example, it may be a lower molecular weight haplotype having a molecular weight of about 1,000 or less (hereinafter, referred to as "monomeric N,N-dialkylhalfcaquinone"). Further, it may be an oligomer or a polymer having a relatively high molecular weight of about 1,000 or more, and an oligomer type or a polymer type having an N,N-dialkylcarbazone at the terminal (hereinafter, referred to as It is "a polymer having an N,N-dialkylhalf-anthracene at the end"). Further, it is also preferred to use a monomeric N,N-dialkylhalocarbamate and a polymer having an N,N-dialkylhalfquinone at the terminal.

Preferred specific examples of the "monomeric N,N-dialkylcarbazone" include, for example, 1,6-hexamethylenebis(N,N-dimethylhalocanthene), 4, 4'-(methylenedi-p-phenylene) bis(N,N-dimethylhalocyanine), 4,4'-(methylenedi-p-phenylene) bis(N, N-diethylcarbazone), 4,4'-(methylenebis-p-phenylene)bis(N,N-di-iso-propylhalocyanine), α,α-(pair - Benzyl) bis(N,N-dimethylhalocanthene), 1,4-cyclohexyl bis(N,N-dimethylhalocanthine), biuret-three (hexamethylene) Base-N,N-dimethylsemicarbazide, and the like. Particularly preferred are 1,6-hexamethylenebis(N,N-dimethylhalocyanine), 4,4'-(methylenebis-p-phenylene)bis (N,N-di Methyl half-calendar).

Preferred specific examples of the "polymer having an N,N-dialkylcarbazone at the end" include, for example, in the use of a polyurethane elastic yarn. The antioxidant is a well-known polycarbamate or polyurethane-urea prepared from a third-stage nitrogen-containing diol and a third-stage nitrogen-containing diamine and an organic diisocyanate. It contains a polymer of an N,N-dialkylhalfquinone terminal group or the like. A compound having a third-stage nitrogen in the main chain and having an N,N-dialkylhalf-carboxin at the end is capable of exhibiting a high dyeing even if it is a low concentration of N,N-dialkylcarbazone. The heat resistance can be made to be high elastic recovery and high tensile strength when it is not mixed.

Preferred specific examples of the "third-stage nitrogen-containing diol" include, for example, N-methyl-N,N-diethanolamine, N-methyl-N,N-dipropanolamine, N-methyl-N,N-diisopropanolamine, N-butyl-N,N-diethanolamine, N-tertiary-butyl-N,N-diethanolamine (hereinafter, abbreviated as "TBDEA" .), N-octadecane-N,N-diethanolamine, N-benzyl-N,N-diethanolamine (hereinafter, abbreviated as "BDEA".), N-tertiary-butyl-N, N-diisopropanolamine, and bishydroxyethylperazine can also be used. Dihydroxyisopropyl piperazine Piper derivative. Among them, the most excellent one is TBDEA or BDEA.

Preferred specific examples of the "diamine containing a third-stage nitrogen" include, for example, N-methyl-3,3'-iminobis(propylamine) (hereinafter, simply referred to as "MIBPA"). N) butyl-amino bis-propylamine, N-methyl-amino bis-ethylamine, N-tertiary-butyl-amino bis-propylamine, piperazine -N,N'-bis(3-aminopropyl) (hereinafter, abbreviated as "BAPP".), piperazine -N,N'-bis(2-aminoethyl) and the like. Among them, the best one is MIBPA or BAPP.

Preferred specific examples of the organic diisocyanate are, for example, usable: PICM (methylene-bis(4-cyclohexyl isocyanate)), isophorone diisocyanate (hereinafter, abbreviated as "IPDI"), "diamine diisocyanate, DDI derived from dimer acid, etc." Group diisocyanate" and the like. Among them, the best is PICM or IPDI.

Further, in order to react with the organic diisocyanate to form a terminal halocenyl group, it is preferred to use a substituted anthracene. Preferred specific examples of the "substituted oxime" include, for example, N,N-dimethylhydrazine (hereinafter, abbreviated as "UDMH"), N,N-diethylhydrazine, N, N-dipropyl hydrazine, N,N-diisopropyl hydrazine, N,N-dibutyl fluorene, N,N-diisobutyl fluorene, N,N-dihydroxyethyl hydrazine (hereinafter, referred to as It is "UDHEH".), N,N-dihydroxyisopropyl hydrazine, and the like. Among them, the most excellent one is UDMH or UDHEH.

A polymer comprising an N,N-dialkylcarbazone terminal group in a polyurethane or a polyurethane-urea, preferably by reacting an isocyanate terminal prepolymer with N, N - Dialkyl hydrazine, which has been prepared by adding a stoichiometric amount of hydrazine to allow it to react completely before adding other chain terminators.

The average molecular weight of the polymer having an N,N-dialkylcarbazone at the end is preferably 1,000 or more and 20,000 or less. Further, it is preferred to have an N,N-dialkyl half card at the end per 1 kg. In the polymer of ruthenium, the semi-carboxy group is contained in the range of 0.1 to 100 milliequivalents (meq/kg).

Among them, from the viewpoint of homogenizing the viscosity of the raw material spinning solution of the polyurethane yarn to obtain good spinnability, it is preferred to contain the N,N-dialkylhalocyanine terminal group. In polyurethane or polyurethane-urea The polymer. Further, in order to effectively exhibit high spinning speed, heat resistance during dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, it is preferred to contain a certain amount of N,N-dioxane. The carbaryl compound is preferred, but it is preferably not excessive from the viewpoint of obtaining a more excellent basic physical property as a polyurethane yarn. In general, the content thereof is preferably in the range of 0.1% by weight or more and 6.0% by weight or less. Further, the content may be appropriately determined depending on the application in advance by an appropriate test.

Further, a preferred compound (b) required for producing a polyurethane elastic yarn which is particularly resistant to heat resistance at high temperature dyeing comprises: reacting UDMH to an addition polymerization of TBDEA and PICM The compound is obtained by polymerizing the isocyanate end of the polyurethane prepolymer obtained by a ratio of 2:3 to 20:21 to form a compound obtained by dimethylhalocyanine; or UDMH The compound obtained by reacting a mixture of MIBPA and PICM with a PIMC series of a polyurethane-urea prepolymer having a composition of 2:3 to 20:21 to form a dimethylhalocyanine. Further, in order to obtain a heat-resistant polyurethane elastic yarn which is subjected to a heat history in which a high-temperature dyeing process is repeatedly performed, it is preferred to use a N,N-dialkylhalocyanine compound as a monomer type. 1,6-hexamethylenebis(N,N-dimethylhalocan) or 4,4'-(methylenedi-p-phenylene) of N,N-dialkylcarbazone Bis(N,N-dimethylsemicarbazide) and used to react UDMH to the end of a polyurethane composed of TBDEA and PICM as described above to form a dimethyl half card a compound of hydrazine; or a polyamine group consisting of a mixture of MIBPA and PICM and a PICM by reacting UDMH a terminal of a formate-urea such that it forms a dimethyl half-carbocyclic polymer having an N,N-dialkylcarbazone at the end, and contains a semi-carboxy group per 1 kg of yarn. A range of 0.1 to 200 milliequivalents (meq/kg).

The "(c) compound" used in the present invention, that is, the "nitrogen-containing aromatic compound" is a compound having a nitrogen-containing aromatic heterocyclic ring in which a nitrogen atom is disposed in an aromatic ring in the molecule. The "chemical structure skeleton" includes: pyrrole having a nitrogen-containing aromatic heterocyclic ring, pyridine, oxazole, quinoline; imidazole, pyrazole, hydrazine having a dinitrogen-containing aromatic heterocyclic ring Pyr , pyrimidine, naphthyridine, phenanthroline; trinitrogen with an aromatic heterocycle containing trinitrogen A benzotriazole or a naphthyridine may be a hetero atom other than nitrogen such as benzothiazole or benzoxazole. Specific examples of such nitrogen-containing aromatic compounds are preferably benzotriazole compounds or trinitrogens which are well known as ultraviolet absorbers. The compounds, more specifically, include: 2-(3,5-di-tris-pentyl-2-hydroxyphenyl)benzotriazole, 2-(3-tris-butyl-2-hydroxyl) Phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-bisphenyl)benzotriazole, 2,4-di(2',4'-dimethylphenyl) -6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole , 2,2'-(1,4-phenylene) bis[4H-3,1-benzaldehyde a compound such as 4-keto]. If listed under the trade name, it includes: "TINUVIN"-P, "TINUVIN"-213, "TINUVIN"-234, "TINUVIN" manufactured by Ciba Geigy/Co., Ltd. 327, "TINUVIN"-328, "TINUVIN"-571;"Sumisorb" 250 manufactured by Sumitomo Chemical Co., Ltd.; "CYASORB" manufactured by American Cyanamid Co. UV-5411, UV-1164, UV-3638; "ADEKASTAB" LA-31 manufactured by Asahi Denka Kogyo KK.

As described above, it is desired to produce a polyurethane elastic yarn which exhibits high heat resistance at the time of dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, and has high elastic recovery and high elongation. Then, the content of the compound (c) must be 0.01% by weight or more and 0.30% by weight or less.

The compound (c) is a compound group having a molecular weight of 300 or more from the viewpoint of suppressing the amount of volatilization in spinning, as described above. Further, from the viewpoint of improving heat resistance and spinnability at the time of dyeing, a compound having two or more nitrogen atoms in the aromatic ring is more preferable. It can be considered that the chelate compound function is exhibited because it is easy to form a complex with a heavy metal. If the effect is to be further exerted, it is preferred that the chemical structure skeleton of the (c) nitrogen-containing aromatic compound is trinitrogen. . Further, the content of the compound (c) is preferably in the range of 0.01% by weight or more and 0.30% by weight or less, and is preliminarily tested according to the molecular weight of the compound (c) actually used, the effective nitrogen number of the aromatic ring, or the like. To properly determine the optimum value.

Further, in order to produce a polyurethane elastic yarn particularly having high heat resistance during dyeing, the compound (c) is preferably 2,4-bis(2',4'-dimethylphenyl)- 6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole . As mentioned above, the compound (a) uses 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three. nitrogen -2,4,6(1H,3H,5H)-trione, and using 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkane Oxyphenyl)-1,3,5-triazole As the compound (c), a synergistic effect which is particularly high in heat resistance at the time of dyeing can be obtained.

Further, as a compound used in the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound, for example, the dispersion and dissolution of the polyurethane are accelerated, and the produced polyaminocarboxylic acid is produced. The ester yarn imparts the desired characteristics and can be made into a moderately transparent polyurethane yarn, further reducing the content of such compounds even when the spinning process is subjected to heat, etc., and does not cause yarn From the viewpoint of discoloration and the like, it is preferred that N,N'-dimethylacetamide (hereinafter, abbreviated as "DMAc") at 20 ° C or a 20% by weight solution of DMF has a viscosity of 10 cP or more and 10,000. P liquid below P.

Further, the polyurethane used in the present invention is preferably one type or a mixture of two or more types of terminal blocking agents. The "end-capping agent" is preferably: dimethylamine, dipropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, "monoamine" such as dipropylamine, butylmethylamine, isobutylmethylamine, isoamylmethylamine, dibutylamine, dipentylamine; ethanol, propanol, butanol, isopropanol, alkenyl "monohydric alcohol" such as propyl alcohol or cyclopentanol; "monoisocyanate" such as phenyl isocyanate.

Further, in the present invention, it is also possible to contain various kinds of polyurethane elastomer or polyurethane spinning solution in addition to those described above, without hindering the effects of the present invention. Stabilizers such as "antioxidants" such as sterically hindered phenolic, sulfuric, and phosphorus; sterically hindered amines, triazoles, benzophenones, benzoates, nickels, and salicyl "Light stabilizer" such as "molecular stabilizer" for antistatic agents, lubricants, peroxides, etc. Metal inerting agent, organic and inorganic nucleating agent, neutralizing agent, fluorescent whitening agent, filler, flame retardant, flame retardant, pigment, etc. For example, a light stabilizer, an antioxidant, or the like contains a 2,6-di-tertiary-butyl-p-cresol (BHT) or benzophenone-based agent, various hindered amine-based agents, iron oxide, and titanium oxide. Inorganic substances such as various pigments, zinc oxide, cerium oxide, magnesium oxide, carbon black, metal soaps such as fluorine-based or polyoxynoxy resin powders, magnesium stearate, and the like, containing silver or zinc or the like Other such as a fungicide, a deodorant, a fungicide, a lubricant such as polyoxymethylene or mineral oil, an antistatic agent such as barium sulfate, barium oxide, betaine or a phosphate system, etc., and the like, It is also preferred that the polymer reacts with these. Further, from the viewpoint of easily accelerating the spinning speed in the dry spinning process, metal oxide fine particles such as titanium oxide or zinc oxide can be added to the spinning dope. Further, from the viewpoint of improving heat resistance or functionality, it is also possible to add inorganic or inorganic porous substances (for example, bamboo charcoal, charcoal, carbon black, porous mud, clay, diatoms) without impeding the efficacy of the present invention. Earth, coconut shell activated carbon, coal-based activated carbon, zeolite, pearlite, etc.).

These other additives may also be added when the spinning dope is prepared by mixing the polyurethane solution with the modifier as described above, or may be included in advance before mixing. In the polyurethane solution or in the dispersion. The content of these additives is appropriately determined depending on the purpose and the like.

Next, the manufacturing method of the polyurethane elastic yarn of the present invention will be described in detail.

In the present invention, it is preferred to first produce a polyurethane solution. Method for producing a polyurethane solution, or a solute of a solute in a solution It may be any one of a melt polymerization method, a solution polymerization method, or the like. However, it is more preferred to be a solution polymerization method. In the case of the solution polymerization method, since a small amount of foreign matter such as a gel is generated in the polyurethane, it is easy to spin, and it is easy to produce a fine-density polyurethane yarn. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.

Further, the polyurethane which is particularly suitable for the present invention includes: using PTMG having a molecular weight of 1,000 or more and 6,000 or less as a polymer diol, using MDI as a diisocyanate, and using ethylene glycol, 1, 3 - at least one of propylene glycol, 1,4-butanediol, ethylenediamine, 1,2-propylenediamine, and 1,3-propanediamine is synthesized as a segment growth agent, and the melting point of the high temperature side is 200 ° C or more, 300 ° C or less.

These polyurethanes can be obtained, for example, by synthesis using a raw material as described below in a solvent containing DMAc, DMF, DMSO, NMP or the like as a main component. For example, each raw material is added to these solvents and dissolved, and heated to a suitable temperature to carry out a reaction to form a so-called "one-shot process" of a polyurethane. Further, the polymer diol and the diisocyanate are first melt-reacted, and then the reactant is dissolved in a solvent to be reacted with a diol or the like of the chain extender as described above to prepare a polyamino group. A method of an acid ester or the like can be employed in a particularly suitable method.

When the segment growth agent is a low molecular weight diol, a representative method for the high temperature side melting point of the polyurethane to be in the range of 200 ° C or more and 300 ° C or less includes controlling the polymer diol, MDI, low molecular A method of measuring the type and ratio of diols. For example, when the molecular weight of the polymer diol is low, the ratio of MDI is relatively increased, whereby a high-melting-point polyurethane having a high melting point can be obtained. Further, similarly, when the molecular weight of the low molecular weight diol is low, the ratio of the high molecular weight diol is relatively reduced, whereby a polyurethane having a high melting point on the high temperature side can be obtained. When the molecular weight of the polymer diol is 1,800 or more, if the melting point of the high temperature side is 200 ° C or more, it is preferably (Mole of MDI) / (mole of polymer diol) = 1.5. The above ratios are aggregated.

Further, in the case of synthesizing these polyurethanes, it is preferred to use one or a mixture of two or more kinds of catalysts such as an amine-based catalyst or an organic metal catalyst.

The "amine-based catalyst" includes, for example, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethyl Morpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N', N'-tetramethylhexamethylenediamine, bis-2-dimethylaminoethyl ether, N,N,N',N',N'-pentamethyldiethylenetriamine, tetramethylguanidine, Tri-ethylenediamine, N,N'-dimethylper , N-methyl-N'-dimethylaminoethyl-peri , N-(2-dimethylaminoethyl)morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N,N-dimethylaminoethanol, N,N,N'- Trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)per 2,4,6-gin(dimethylaminomethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, and the like.

Further, the "organometallic catalyst" includes tin octylate, dibutyltin dilaurate, and dibutyl lead octoate.

Polyamine group in a polyurethane solution prepared as described above The concentration of the formate is usually preferably in the range of 30% by weight or more and 80% by weight or less.

In the present invention, it is preferred to add the compound (a), the compound (b) and the (c) nitrogen-containing aromatic compound as described above in a predetermined amount in the polyurethane solution. As a polyurethane spinning solution. The method of adding the compound (a), the compound (b), and (c) the nitrogen-containing aromatic compound to the polyurethane solution may be any method. The representative method is a method using a static mixer, a method of stirring, a method using a homomixer, a method using a twin-screw extruder, and the like. However, the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound are preferably prepared as a solution from the viewpoint of achieving uniform addition to the polyurethane solution. Add to.

Further, since the addition of the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound to the polyurethane solution may cause the solution viscosity of the mixed solution after the addition, and the polyamine before the addition. The viscosity of the solution of the carbamate will be higher than expected. Therefore, from the viewpoint of preventing this phenomenon, it is preferred to use dimethylamine, dipropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, Dipropylamine, butylmethylamine, isobutylmethylamine, isoamylmethylamine, dibutylamine, dipentylamine, etc. "monoamine"; ethanol, propanol, butanol, isopropanol, The "monohydric alcohol" such as allyl alcohol or cyclopentanol; the terminal blocking agent such as "monoisocyanate" such as phenyl isocyanate may be used alone or in combination of two or more.

Adding (a) compound, (b) compound to the polyurethane solution When the compound (c) and the nitrogen-containing aromatic compound are added, a chemical agent such as a light stabilizer or an antioxidant, or a pigment may be added as described above.

Further, the polyurethane spinning solution is spun, whereby the polyurethane elastic yarn of the present invention can be obtained.

In the present invention, the fineness, the number of filaments, the cross-sectional shape, and the like of the polyurethane elastic yarn are not particularly limited. For example, the yarn system may be a monofilament composed of one monofilament or a multifilament composed of a plurality of monofilaments. The cross-sectional shape of the yarn may be round or flat.

Further, the method of solution spinning is not particularly limited, and any method can be applied. However, from the viewpoint of obtaining a yarn having a smooth surface and high elongation, high recovery, and high heat resistance, Dry spinning is preferred.

In addition, the residual deformation ratio (ie, the setting property) and the stress relaxation ratio of the polyurethane elastic yarn are susceptible to the conditions of the spinning process, particularly the guide rolls. (godet roller) and the speed ratio of the coiler. Therefore, the conditions of the speed ratio should be appropriately determined according to the purpose of use of the yarn.

That is, from the viewpoint of obtaining a polyurethane elastic yarn having a residual deformation ratio and a stress relaxation ratio which is desired, it is preferable that the speed ratio of the guide roller to the winder is 1.15 or more. The range below 1.65. Further, in particular, in order to obtain a polyurethane elastic yarn having a low residual deformation ratio and a low stress relaxation rate, the speed ratio of the guide roller to the winder is preferably in the range of 1.15 or more and 1.4 or less, and Further preferably more than 1.15, The range below 1.35. On the other hand, in order to obtain a polyurethane elastic yarn having a high residual deformation ratio and a high stress relaxation rate, the speed of the guide roller and the winder is preferably in the range of 1.25 or more and 1.65 or less, and More preferably, it is in the range of 1.35 or more and 1.65 or less.

In addition, since the strength of the polyurethane elastic yarn can be increased by increasing the spinning speed, if a spinning speed of 450 m/min or more is used, an appropriate strength can be obtained in practical applications. A standard elastic yarn is therefore preferred. Further, it is preferably a spinning speed of about 450 to 1,000 meters per minute in consideration of industrial production.

"Embodiment"

The invention will be described in more detail by way of examples.

The breaking strength, elongation at break, residual deformation ratio, stress relaxation rate, heat resistance at the time of dyeing, appearance quality showing general heat resistance, and thermosoftening point of the polyurethane elastic yarn of the present invention are measured. The law is explained.

<Residual deformation rate, stress relaxation rate, breaking strength, elongation at break> The residual deformation rate, the stress relaxation rate, the breaking strength, and the elongation at break were measured by performing a tensile test using a INSTRON Model 5564 tensile tester.

The sample having a sample length of 5 cm (L1) was subjected to 300% elongation by 5 times at a tensile rate of 50 cm/min, and the stress at the 300% elongation at the 5th time was assumed to be (G1). Secondly, the length of the sample was maintained at 300% elongation for 30 seconds. Assume that the stress after 30 seconds is maintained as (G2). Second, return the elongation of the sample and assume that the stress becomes zero. The length of the sample is (L2). The 300% stretching, holding, and recovery operations were repeated, and the stretching was performed until the sample was cut at the sixth stretch. It is assumed that the stress at the time of the fracture is (G3), and the length of the sample at the time of the fracture is (L3). Hereinafter, the characteristics as described above can be calculated as follows: breaking strength (cN) = (G3); stress relaxation rate (%) = 100 × ((G1) - (G2)) / (G1) ; residual deformation rate (%) = 100 × ((L2) - (L1)) / (L1); elongation at break (%) = 100 × ((L3) - (L1)) / (L1).

<Heat resistance at the time of dyeing 1 (resistance of a nylon-mixed fabric having a low dyeing temperature in a state in which unsaturated fatty acids and heavy metals are attached) Polyamide long fibers (24 dtex, 7 filaments) and 15% by weight manufactured by Toray Industries, Inc., manufactured by Toray Industries, Inc., were manufactured by a general knitting method. The polyurethane warp yarn (20 dtex) consists of a machine with a wale of 11/inch (11/2.54 cm) and a course of 25/inch (25/). Two-way half tricot stitches of 2.54 cm) are used as knitted raw fabrics.

The prepared knitted fabric was pre-formed under the conditions of 170 ° C, 60 seconds, 3% elongation, and then 0.1 ml of the drug 1 was applied, followed by coating (about substantially simultaneously, or within 1 minute) 0.1 ml of the drug. After 2, Perform dry heat treatment (after 175 ° C, dry heat treatment for 60 seconds, temporarily take out and dissipate heat to room temperature, dry heat treatment at 180 ° C for 60 seconds), and secondly, alternate 20% elongation in both vertical and horizontal directions. The test was performed with a bending tester of 2 times/second. Further, the pharmaceutical 1 is a mineral oil-based nylon spinning oil containing 1% oleic acid. For the drug 2, an aqueous copper acetate solution (copper concentration of 100 ppm) was used. The knitted fabric of the drug 1 and the drug 2 adhered as described above is reproduced in a typical case. The nylon-based stretchable knitted fabric at the stage before dyeing has a small amount of mechanical oil (with metal mixed) during knitting. In the case where the nylon was adhered to the spin finish, the amount of adhesion to the drug 1 of 0.9 g of the knitted fabric was 3.0 mg, and the amount of the drug 2 was 3.0 mg.

The obtained stretchable fabric was dyed by a conventional method. That is, a dyeing solution of 1.0% owf (by weight of fabric) of Kayanol Milling Blue 2RW (manufactured by Nippon Kayaku Co., Ltd.) at a flow rate of 98 ° C Dyeing by staining.

After visual observation or enlargement, the degree of damage of the polyurethane structure of the dyed stretch fabric produced was observed and judged on the following basis. In addition, the judgment is made by 5 people and the most frequent value (the most frequently occurring judgment) is used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".

A: no damage; B: loss of elasticity and depression phenomenon observed on the grey fabric, and if enlarged, the polyurethane elastic yarn has been embrittled; C: There is a hole in the cloth.

<Heat resistance at the time of dyeing 2 (resistance of nylon mixed fabric with low dyeing temperature for repeated dyeing)> In order to evaluate the heat aging resistance when the polyurethane yarn was subjected to high temperature dyeing, a test for subjecting the polyurethane yarn to a high temperature liquid treatment in the following manner was carried out. Further, the breaking strength was measured for the polyurethane yarn after the high temperature liquid treatment, and the retention ratio was calculated.

The polyurethane yarn was fixed in a state of 100% elongation, and after applying a predetermined type (170 ° C, 60 seconds), it was left untensioned at room temperature for 24 hours, and then as before. The method described is used to determine the breaking strength (G3) in the same manner. Further, after the predetermined type was applied, it was sealed in a pressure vessel containing 98 ° C of high-temperature water in a fixed state, and treated in a high-temperature liquid for a total of three times in a set of 98 ° C for 60 minutes. At this time, after the treatment in the first high temperature liquid and after the second high temperature liquid treatment, the samples are temporarily taken out from the pressure vessel, and are allowed to dissipate heat to room temperature, and then applied to the next high temperature liquid. The polyurethane film treated in the third high temperature liquid was taken out from the pressure vessel, allowed to stand in an untensioned state at room temperature for 24 hours, and then the fracture was measured in the same manner as described above. Strength (G5). The ratio (breaking strength retention ratio) of the rupture strength (G5) of the yarn after the treatment in the third high-temperature liquid with respect to the breaking strength (G3) of only the predetermined type of yarn is calculated as an index of heat resistance 2 : breaking strength retention ratio (%) = 100 × (G5) / (G3).

<The heat resistance at the time of dyeing 3 (the polyester mixed fabric with a higher dyeing temperature is in the Resistance to unsaturated fatty acids and heavy metals) Polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc., 82% by weight, and 18% by weight of polyurethane were produced by a general knitting method. The elastic yarn (22 dtex) consists of two lines of semi-finished warp knitting with 13/inch (13/2.54 cm) and 30/inch (30/2.54 cm) weft on the machine. As a knitted fabric.

The prepared knitted fabric was preliminarily prepared under the conditions of 190 ° C, 60 seconds, and 3% elongation, and then 0.1 ml of the drug 1 was applied, followed by (substantially simultaneously or within 1 minute), and 0.1 ml of the drug was applied. 2, after the dry heat treatment (after 195 ° C, 60 seconds of dry heat treatment, temporarily taken out and cooled to room temperature, dry heat treatment at 200 ° C, 60 seconds), and then used in the vertical and horizontal directions The test was carried out with a bending tester of up to 20% elongation and 2 times/second. Further, as the drug 1, a spinning oil agent for mineral oil-based polyester containing 1% oleic acid is used. For the drug 2, an aqueous solution of copper citrate (copper concentration of 100 ppm) was used. The knitted fabric of the drug 1 and the drug 2 adhered as described above is a mechanically stretched nylon fabric which is reproduced in a typical case before the dyeing process, and has a slight amount of mechanical oil (when metal is mixed). When it is adhered to the spinning oil agent for nylon, the adhesion amount to the drug 1 of 1.0 g of the knitted fabric is 3.0 mg, and the adhesion amount of the drug 2 is 3.0 mg.

The obtained stretchable fabric was dyed by a conventional method. That is, the high-energy disperse dye "Dianix" Black HG-FS conc (made by Dystar Textilfarben GmbH) containing 4% owf Manufactured, and 1% owf of POE alkylamine ether sulfate (sulfated) "NEWBON WS" (a levelling agent manufactured by Nicca Chemical Co., Ltd.) And dyeing to a pH 5 dye bath by a buffer of ester acid and sodium acetate, and dyeing at 125 ° C for 60 minutes.

Next, it contains 2 g/L of low sodium sulfite (hydrosulfite), a special anionic surfactant "Senkanol CW" (soaping agent manufactured by Senka Co. Ltd.), and 1 g/liter. The sodium hydroxide treatment bath was subjected to reduction washing at 70 ° C for 20 minutes.

After visual observation or amplification, the degree of damage of the polyurethane structure of the dyed stretch fabric produced was observed and judged on the following basis. In addition, the judgment is made by 5 people and the most frequent value (the most frequently occurring judgment) is used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".

A: no damage; B: loss of elasticity and sag phenomenon observed on the grey cloth, when the magnified observation, the polyurethane elastic yarn is already embrittled; C: the cloth has a through hole.

<Heat resistance at the time of dyeing 4 (resistance of repeated dyeing of polyester mixed fabrics with higher dyeing temperature) In order to evaluate the heat aging resistance when the polyurethane yarn was subjected to high temperature dyeing, the polyurethane yarn was subjected to a high temperature liquid treatment as described below. And, for the polyurethane yarn after the high temperature liquid treatment Determine the breaking strength and calculate the retention rate.

The polyurethane yarn was fixed in a state of 100% elongation, and after applying a predetermined type (190 ° C, 60 seconds), it was left untensioned at room temperature for 24 hours, and then as before. The method described is used to determine the breaking strength (G3) in the same manner. Further, after the predetermined type was applied, it was sealed in a pressure vessel containing 130 ° C of high-temperature water in a fixed state, and treated in a high-temperature liquid for three times in total at 130 ° C for 60 minutes. At this time, after the treatment in the first high temperature liquid and after the second high temperature liquid treatment, the samples are temporarily taken out from the pressure vessel, and are allowed to dissipate heat to room temperature, and then applied to the next high temperature liquid. The polyurethane film treated in the third high temperature liquid was taken out from the pressure vessel to make it untensioned, left at room temperature for 24 hours, and then measured in the same manner as described above. Breaking strength (G5). The ratio (breaking strength retention ratio) of the rupture strength (G5) of the yarn after the treatment in the third high-temperature liquid with respect to the breaking strength (G3) of only the predetermined type of yarn is calculated as an index of heat resistance 4 : breaking strength retention ratio (%) = 100 × (G5) / (G3).

<Appearance quality> In the test of heat resistance 1 at the time of dyeing as described above or the heat resistance 3 at the time of dyeing, dyeing was performed in the same manner except that the coating and bending tests of the drug 1 and the drug 2 were not carried out. Flexible fabric. That is, after the knitted fabric is produced, a predetermined type, a dry heat treatment, and a dyeing treatment are applied to produce a dyed stretch fabric. For the dyed stretch fabric (width of 1.8 meters, length of about 20 meters), The appearance of the grey fabric was examined, and the polyurethane structure was magnified and judged on the following basis: In addition, the judgment was carried out by 5 persons, and the most frequent value (the most frequently judged) was used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".

A: no waviness or streaky defect, the structure is also homogeneous; B: has local corrugation or stripe-like defects, and is less than one place every 20 meters; C: has ripple or stripe defects, and each 20 meters is more than one place.

<thermal softening point> The thermal softening point was measured as one of the heat setting indexes of the polyurethane yarn. The polyurethane elastic yarn was subjected to measurement of the temperature distribution of the dynamic storage elastic modulus E' at a temperature increase rate of 10 ° C/min using a dynamic elastic modulus measuring machine RSAII manufactured by Rheometric Scientific, Inc. . The thermal softening point is measured by the intersection of a tangent line in a flat region of 80 ° C or more and 130 ° C or less in the E' curve, and a tangent to the E' curve which is lowered by heat softening at 160 ° C or higher. In addition, E' uses a logarithmic axis and temperature uses a linear axis.

(Content of each compound) One gram of the yarn sample was prepared and charged in a Soxhlet's extractor using methylene chloride as a solvent for extraction for 60 minutes or more, and the extract was temporarily dried, and then methanol was used. The extraction was carried out in the same manner, and then each compound was isolated by high performance liquid chromatography (HPLC). The structure is determined by a conventional method such as ¹ H NMR, and each of the isolated and determined structures is preliminarily measured by high performance liquid chromatography, and the content is calculated by the following formula: content (% by weight) = (sample) Crest area/measured peak area) × (quantity test material weight / yarn sample weight).

[Example 1]

Polymerization of PTMG, MDI and ethylene glycol having a molecular weight of 2,900 was carried out by a conventional method to prepare a DMAc solution (35 wt%) of a polyurethane resin. This was taken as the polymer solution A1.

Next, (a) a hindered phenol compound, (b) an N,N-dialkylhalocyanine compound, and (c) a nitrogen-containing aromatic compound are respectively used as (a1) 1,3,5-para ( 4-tertiary-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a dimethyl half card at the end Polymer of ruthenium, (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5 - three nitrogen (Molecular weight: 509; "Cyasorb" (registered trademark) UV-1164, manufactured by CYTEC Industries Inc.), and these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B1.

The polymer solution A1 and the additive solution B1 were respectively 94.9% by weight. And the ratio of 5.1% by weight was uniformly mixed to serve as the spinning solution D1.

The spinning solution D1 was dry-spun at a spinning speed of 1.40 at a set guide roller and a coiler, and was taken up at a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbamate elastic yarn (200 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.

Then, the elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 2.

From the obtained polyurethane elastic yarn (20 dtex) and nylon long fiber (24 dtex, 7 filament) manufactured by Toray Industries Co., Ltd., manufactured by a general knitting method, made of 85% by weight of nylon Long-fiber and 15% by weight of polyurethane elastic yarns are machined on a machine with a number of turns of 11/inch and a machine with a number of laps of 25/inch. Grey fabric (Nylon-based stretch fabric). In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn when it was repeatedly dyed was evaluated by the test of heat resistance 2 at the time of dyeing.

Breaking elongation, breaking strength and residual change of polyurethane elastic yarn The thermosoftening point of the index of shape rate, stress relaxation rate, and heat setting property is the same as that of Comparative Example 1 (described later) of the unmixed (b) compound and the compound (c), and is in processability or gray cloth. The adverse effects of mixing such additives have not been observed in terms of properties.

In addition, the heat resistance of the nylon-based stretchable fabric at the time of dyeing includes heat resistance 1 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), heat resistance at the time of dyeing 2 (resistance to repeated dyeing) The internal comparison of Comparative Example 1 showed a significant increase. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.

[Example 2]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used (a1) 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-dimethyl Benzomethyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, and (a2) an addition polymer of divinylbenzene and p-cresol (Methacrol, manufactured by EI du Pont de Nemours and Company) (registered trademark) 2390), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a dimethyl semi-carbosome at the end Polymer, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5 - three nitrogen And these were mixed at a ratio of 1.0:1.0:3.0:0.15, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B2.

The polymer solution A1 prepared in Example 1 and the additive solution B2 as described above were uniformly mixed at a ratio of 94.85% by weight and 5.15% by weight, respectively, to obtain a spinning solution D2.

The spinning solution D2 was dry-spun and coiled at a spinning speed of 1.40 and a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbide elastomer yarn (200 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.15% by weight, respectively.

Two lines of the same line as in the case of Example 1 were produced from the obtained polyurethane elastic yarn (20 dtex) and the nylon long fiber (24 dtex, 7 wire) manufactured by Toray Industries, Ltd. Semi-warp warp organization for use as a knitted fabric (Nylon-based stretch fabric). In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn when it was repeatedly dyed was evaluated by the test of heat resistance 2 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative example 1 (as after The) is the same, and in terms of processability or fabric properties, no adverse effects caused by mixing the additives are observed.

In addition, the heat resistance of the nylon-based stretchable fabric at the time of dyeing includes heat resistance 1 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), heat resistance at the time of dyeing 2 (resistance to repeated dyeing) The internal comparison of Comparative Example 1 showed a significant increase. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.

[Example 3]

The PTMG, MDI, ethylenediamine, and terminal chain-blocking diethylamine having a molecular weight of 1,800 were polymerized by a conventional method, and a DMAc solution of a polyurethane-urea polymer (35 wt%) was prepared. . This was taken as the polymer solution A2.

Next, (a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used as (a1) 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-). Dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, and (a2) an addition polymer of divinylbenzene and p-cresol ("Methacrol" (registered trademark) 2390, manufactured by DuPont), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a polymer of dimethylhalocyanine at the terminal, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazo And these were mixed at a ratio of 1.0:1.0:3.0:0.10, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B3.

The polymer solution A2 and the additive solution B3 were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D3. The spinning solution D3 was dry-spun and wound up at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce 22 dtex and 2 filaments. Polyfilament elastic yarn of a multifilament (500 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd. by a general knitting method. The number of on-machine passes consisting of 82% by weight of polyethylene terephthalate long fibers and 18% by weight of polyurethane elastic yarn is 13/inch, and the number of on-board laps is 30/ The two-inch in-line half-warp warp organization is used as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of Comparative Example 2 (described later) in which the compound (b), the compound (c), and the like are not mixed, and are in processability or In terms of the characteristics of the fabric, no adverse effects caused by the mixing of the additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.

[Example 4]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), and (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-phenylphenyl)propionate], in the examples (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (b2)4,4 '-(Methylene di-p-phenylene) bis(N,N-dimethylhalocyanine), and (c1) 2,4-di(2',4'-dimethylphenyl) -6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:2.0:0.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B4.

The polymer solution A2 prepared in Example 3 and the additive solution B4 as described above were uniformly mixed at a ratio of 95.4% by weight and 4.6% by weight, respectively, to obtain a spinning solution D4.

The spinning solution D4 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 2.5% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is Both of them were the same as Comparative Example 2 (described later) in which the (b) compound and the compound (c) were not mixed, and no adverse effects caused by mixing the additives were observed in terms of processability or fabric properties.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 5]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], and (a4) Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), used in Example 4 (b2) 4,4'- (Asia Methyl di-p-phenylene) bis(N,N-dimethylhalocyanine), and (c1) 2,4-di(2',4'-dimethylphenyl)-6-( 2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:1.0:1.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B5. And, in addition to the above, a polyurethane formed by the reaction of tris-butyldiethanolamine and methylene-bis(4-cyclohexyl isocyanate) as a stabilizer (DuPont) The DMAc solution (concentration: 35 wt%) of "Methacrol" (registered trademark) 2462) was used as another additive solution Z1 (35 wt%).

The polymer solution A2 prepared in Example 3, the additive solution B5 as described above, and the other additive solution Z1 were uniformly mixed at a ratio of 93.4% by weight, 4.6% by weight, and 2.0% by weight, respectively, as a spinning solution D5. .

The spinning solution D5 was dry-spun at a speed ratio of 1.20 at a set guide roller and a coiler, and was taken up at a spinning speed of 600 meters/minute to produce a 22 dtex, 2 wire multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It contained 3.0% by weight, 1.5% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

And, the polyurethane elastic yarn obtained will be repeated The heat resistance at the time of dyeing was evaluated by the test of heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 6]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], and (a4) Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), used in Example 1 (b1) with TBDEA and PICM 6 a repeater of up to 8 and reacting with UDMH to form a dimethyl half-carbocycle polymer at the end, and (b2) 4,4'-(methylene II) used in Example 4. -p-phenylene)bis(N,N-dimethylhalocyanine), and (c1)2,4-di(2',4'-dimethylphenyl)-6-(2"- Hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:2.0:0.5:2.0:0.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B6.

The polymer solution A2 prepared in Example 3 and the additive solution B6 as described above were uniformly mixed at a ratio of 93.9 wt% and 6.1 wt%, respectively, to obtain a spinning solution D6.

The spinning solution D6 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It contained 3.5% by weight, 2.5% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 7]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:005, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B7.

The polymer solution A2 prepared in Example 3 and the additive solution B7 as described above were uniformly mixed at a ratio of 94.95 wt% and 5.05 wt%, respectively, to obtain a spinning solution D7.

The spinning solution D7 was dry-spun at a speed ratio of 1.20 at a set guide roller and a coiler, and was taken up at a spinning speed of 600 meters/minute to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.05% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

And, the polyurethane elastic yarn obtained will be repeated The heat resistance at the time of dyeing was evaluated by the test of heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, the heat resistance 4 is slightly worse when the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same, and only the amount of addition of c1 is different. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 8]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.15, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B8.

The polymer solution A2 prepared in Example 3 and the additive solution B8 as described above were uniformly mixed at a ratio of 94.85% by weight and 5.15% by weight, respectively, to obtain a spinning solution D8.

The spinning solution D8 was dry-spun and coiled at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.15% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, it will The knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 9]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.20, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B9.

The polymer solution A2 prepared in Example 3 and the additive solution B9 as described above were uniformly mixed at a ratio of 94.80% by weight and 5.20% by weight, respectively, to obtain a spinning solution D9.

The spinning solution D9 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.20% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, when heat resistance 3 and heat resistance 4 are compared with Example 3 in which the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same, and only the addition amount of c1 is different, A little worse. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 10]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.25, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B10.

The polymer solution A2 prepared in Example 3 and the additive solution B10 as described above were uniformly mixed at a ratio of 94.75 wt% and 5.25 wt%, respectively, to obtain a spinning solution D10.

The spinning solution D10 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.25% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). In the case of the knitted fabric, the heat resistance 3 at the time of dyeing was carried out, and the evaluation was attached. Heat resistance when dyed with unsaturated fatty acids and heavy metals. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, when heat resistance 3 and heat resistance 4 are the same as those of (c) the nitrogen-containing aromatic compound, the types and addition amounts of all the additives are the same, and only the addition amount of c1 is different, For the worse. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 11]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390 by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:10:3.0:0.30, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B11.

The polymer solution A2 prepared in Example 3 and the additive solution B11 as described above were uniformly mixed at a ratio of 94.70% by weight and 5.30% by weight, respectively, to obtain a spinning solution D11.

The spinning solution D11 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min, and was wound up to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.30% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 The same situation, the two lines are half-flat Warp knitted tissue as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 12]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a3) triethylene glycol-bis[3-(3-tris-butyl-5-A) used in Example 4, respectively. (4-hydroxyphenyl)propionate], (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 3, and reacting with UDMH to form a dimethyl group at the terminal a polymer of a half-calendar, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-trinitrogen, and these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. DYNO-MIL KDL manufactured by WILLY A. BACHOFEN was used to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. Solution B12.

The polymer solution A2 prepared in Example 3 and the additive solution B12 as described above were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D12.

The spinning solution D12 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 13]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used in the embodiment (a4) exoethyl-1,2-bis(3,3-bis[3-tride] -butyl-4-hydroxyphenyl]butyrate), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 3, and reacted with UDMH to form at the end a polymer of dimethylhalocyanine and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl) -1,3,5-trinitrogen And these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B13.

The polymer solution A2 prepared in Example 3 and the additive solution B13 as described above were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D13.

The spinning solution D13 was dry-spun and wound up at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines are semi-finished, and the knitted fabric (polyester-based stretch fabric) is knitted. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of the unmixed (b) compound and the compound (c), Comparative Example 2 (described later), and in the processability or the grey fabric. In terms of characteristics, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Example 14]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390 by DuPont), (b1) used in Example 1 (b1) having an adduct of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the terminal, and (c2)2 [2'-Hydroxy-3',5'-bis(α,α-methylbenzyl)phenyl]benzotriazole ("TINUVIN" 234, manufactured by Cibajiaji Co., Ltd., molecular weight 448) And these were mixed at a ratio of 1.0:1.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B14.

The polymer solution A2 prepared in Example 3 and the additive solution B14 as described above were uniformly mixed at a ratio of 94.9% by weight and 5.1% by weight, respectively, to obtain a spinning solution D14.

The spinning solution D14 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.

Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of Comparative Example 2 (described later) in which the compound (b), the compound (c), and the like are not mixed, and are in processability or In terms of the characteristics of the fabric, no adverse effects caused by the mixing of the additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, the heat resistance 4 is slightly inferior to the third embodiment in which the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same as those of the case of (c). Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.

[Examples 15 to 20]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And (a1) is from 0.03 wt% to 1.0 wt%, and (a2) is from 0.03 wt% to 6.0 wt%, that is, the total amount of the compound (a) is from 0.06 wt% to 7.0 wt%. In the same manner as in Example 3, a spinning solution was separately produced, and a 22 dtex, 2-filament multifilament polyurethane elastic yarn (500 g of yarn) was produced in the same manner as in Example 3, respectively. Package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 5, and contained: 0.06 wt% to 7.0 wt% of (a) compound, 3.0 wt% (b) a compound, and 0.10% by weight of (c) a nitrogen-containing aromatic compound.

Polyurethane elastomer yarn (23 dtex) manufactured by Dongli Industrial Co., Ltd. and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd., respectively, and examples In the same manner as in the case of 3, a two-way half-warp warp structure was separately manufactured as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of each of the obtained polyurethane elastic yarns during repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric during dyeing is the heat resistance 3 (durability to unsaturated fatty acids and heavy metals) during dyeing, Together with the heat resistance 4 at the time of dyeing (resistance to repeated dyeing), Comparative Example 5 (compared with Comparative Example 2) and the compound (a) which was not mixed was improved. However, the heat resistance 3 and the heat resistance 4 of Examples 15 and 16 are the same as the types and addition amounts of all other additives except that the content of the compound (a) is 0.06% by weight and 0.12% by weight. When comparing Example 3, it is a little worse. Further, the stretchable fabric obtained by dyeing has a superior appearance quality. However, (a) the content of the compound is as small as 0.06% by weight of Example 15, and the content of the compound of (a) is as high as 6% by weight or more of the appearance qualities of Example 19 and Example 20, when compared with Example 3. But it is a little worse.

[Examples 21 to 26]

(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And the composition of the compound (b) can be 0.06 wt% to 7.0 wt%, and the composition shown in Table 7 is used, and the spinning solution is separately produced in the same manner as in the example 3, and respectively and in the same manner as in the example 3 A 22 dtex, 2 filament multifilament polyurethane elastomer yarn (500 g yarn package) was produced in the same manner.

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 7, and contained: 2.0% by weight of the compound (a), and 0.06% by weight to 7.0% by weight. (b) a compound, and 0.10% by weight of (c) a nitrogen-containing aromatic compound.

Polyurethane elastomer yarn (23 dtex) manufactured by Dongli Industrial Co., Ltd. and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd., respectively, and examples In the same manner as in the case of 3, a two-way half-warp warp structure was separately manufactured as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.

Further, the heat resistance of each of the obtained polyurethane elastic yarns during repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.

The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.

In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) , Comparative Example 6 showing Comparative Compound 2 and Unmixed (b) Compound Increase as described later). However, when the heat resistances 3 and 4 of Examples 21 and 22 are compared with Example 3 except that the content of the compound (b) is 0.06 and 0.12, and the type and amount of all other additives are the same, It is a little worse. Further, the stretchable fabric obtained by dyeing has a superior appearance quality. However, the appearance quality of Example 25 and Example 26 is slightly compared with Example 3 except that the content of the compound (b) is 6.0% by weight or more, and the type and amount of all other additives are the same. Poor.

[Comparative Example 1]

The polymer solution A1 prepared in Example 1 and the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (Methacrol (registered trademark) 2390 manufactured by DuPont) The DMAc 35 wt% solution B3 and the other additive solution Z1 prepared in Example 5 were uniformly mixed at a ratio of 96.5% by weight, 1.5% by weight, and 2.0% by weight, respectively, to obtain a spinning solution E1. The spinning solution E1 was dry-spun and coiled at a speed ratio of 1.40 and a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbide elastomer yarn (500 grams of yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the compound (a) contained 1.5% by weight.

The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 10.

The obtained polyurethane elastic yarn was used, and was the same as in Example 1. In the same manner, a nylon-based stretch fabric was produced in the same manner as a knitted fabric. In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. As a result, compared with Examples 1 to 2, it was a large difference.

In addition, the knitted fabric was dyed to evaluate the appearance quality. The localized corrugation of the polyurethane yarn caused by various processing processes was more than 200 per 20 m, which made it unsatisfactory. By.

[Comparative Example 2]

Polymer solution A2 prepared in Example 3, addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (Methacrol (registered trademark) 2390 manufactured by DuPont) The DMAc 35 wt% solution B3 and the other additive solution Z1 prepared in Example 5 were uniformly mixed at a ratio of 965 wt%, 1.5 wt%, and 2.0 wt%, respectively, to obtain a spinning solution E2. The spinning solution E2 was dry-spun and coiled at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the compound (a) contained 1.5% by weight.

The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 10.

The obtained polyurethane elastic yarn was used, and in the same manner as in Example 3 In the same manner, a polyester-based stretch fabric was produced as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 4, it was a large difference.

In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes occurred 66 times per 20 meters, so that it could not be Satisfied.

[Comparative Example 3]

(a) a sterically hindered phenol-based compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (manufactured by DuPont). "Methacrol" (registered trademark) 2390), (a5) N,N-bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propanyl]anthrace (Cibajiaji) "IRGANOX" MD1024), (c2)2[2'-hydroxy-3',5'-bis(α,α-methylbenzyl)phenyl]benzotriazole (Cibajia) manufactured by the company "TINUVIN" 234) manufactured by Kyrgyzstan Co., Ltd., and these were mixed at a ratio of 1.0:1.0:0.7, and then a DMAc solution (35 wt%) thereof was prepared. The preparation of this solution was carried out in the same manner as in Example 1. This solution was used as the additive solution F1.

The polymer solution A2 prepared in Example 3, the additive solution F1 as described above, and the other additive solution C1 prepared in Example 5 were respectively at a ratio of 95.3 wt%, 2.7 wt%, and 2.0 wt%. It was uniformly mixed to serve as a spinning solution E3.

The spinning solution E3 was dry-spun and coiled at a speed ratio of 1.30 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 9, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 0.0% by weight, and 0.7% by weight, respectively. The polyurethane elastic yarn contains a relatively large amount of a benzotriazole-based ultraviolet absorber.

The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn are shown in Table 10.

Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 6, it was a large difference.

In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes occurred at 40 places every 20 meters, so that it could not be Satisfied.

[Comparative Example 4]

(a) Compound, (b) Compound, and (c) Nitrogen-Containing Aromatic Compound (a1) 1,3,5-parade (4-tris-butyl-3-hydroxyl group used in Example 1) -2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6( 1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol used in Example 2 (Methacrol, manufactured by DuPont) (trademark) 2390), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a polymer of dimethylhaloquinone at the end And (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1 used in Example 1. , 3,5-trinitrogen And these were mixed at a ratio of 1.0:1.0:3.0:0.8, and then a DMAc solution (35 wt%) thereof was prepared. The preparation of this solution was carried out in the same manner as in Example 1. This solution was used as the additive solution F2.

The polymer solution A2 prepared in Example 3 and the additive solution F2 as described above were uniformly mixed at a ratio of 94.2% by weight and 5.8% by weight, respectively, to obtain a spinning solution E4.

The spinning solution E4 was dry-spun and wound up at a speed ratio of 1.30 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 9, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.8% by weight, respectively. The polyurethane elastic yarn system contains more trinitrogen It is a UV absorber.

The elongation at break, breaking strength, residual deformation ratio, stress relaxation rate, and thermal softening point of the polyurethane elastic yarn are shown in Table 10.

Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 6, it was a large difference.

In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes was more than 100 per 20 meters, so that it could not be People are satisfied.

[Comparative Example 5]

(a) the compound is not mixed, the (b) compound and (c) the nitrogen-containing aromatic compound are each used in the embodiment (b1) having an overlap of 6 to 8 of TBDEA and PICM. And reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-triazole And the composition shown in Table 9, that is, the compound (a) was not mixed, and at 0% by weight, the spinning solution was separately produced in the same manner as in Example 3, and in the same manner as in Example 3, respectively. A 22 dtex, 2 filament multifilament polyurethane yarn (500 g yarn package) was produced.

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the elongation at break, the breaking strength, and the breaking strength of the polyurethane elastic yarn were measured. The residual deformation rate, the stress relaxation rate, and the thermal softening point are shown in Table 10.

Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 15 to 20, it was a large difference. As for the heat resistance 4, yarn breakage occurs during repeated heat treatment, so that it is greatly deteriorated.

In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the corrugated or striped defects of the polyurethane yarn caused by various processing processes occurred more than 100 per 20 meters, so that the system was Unsatisfactory.

[Comparative Example 6]

(a) the compound, the compound (b) is not mixed, and (c) the nitrogen-containing aromatic compound is used in the (a1) 1,3,5-parade (4-tris-butyl-3) used in Example 3, respectively. -hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol ("Methacrol" (registered trademark) 2390) manufactured by DuPont, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And the composition shown in Table 9 was used, and a spinning solution was separately produced in the same manner as in Example 3, and a polydoxy formic acid of 22 dtex and 2 filaments was produced in the same manner as in Example 3, respectively. Ester elastic yarn (500 g yarn package).

The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the polyurethane elastic yarn was used. The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point were measured and shown in Table 10.

Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with the third embodiment and the examples 21 to 26, the results were significantly worse. As for the heat resistance 4 aspect, it is also a big difference.

As described above, in the presence of the compound (a) and the compound (b), (c) a nitrogen-containing aromatic compound is added, which is heat resistance, particularly for the state in which an unsaturated fatty acid and a heavy metal are attached, or The heat resistance of repeated dyeing has a great influence. That is, in the examples in which the compound (c) was added in the presence of the compound (a) and the compound (b), it was found that the comparative examples 1 and 2 in which the amount of the compound (c) was added was 0% by weight, which was extremely remarkable. Increased heat resistance. Among them, from Examples 1 to 6, Example 8, and Examples 12 to 14, it was found that the addition amount of (c) of from 0.07 to 0.18% by weight is important in exhibiting exceptionally excellent performance. Further, if the amount of addition of (c) is continuously increased, the tendency to lower the heat resistance will be exhibited. In other words, in the case of Comparative Examples 3 and 4 in which the amount of addition of (c) is more than 0.3 for the purpose of improving light resistance and the like, the heat resistance is inevitably lowered to Comparative Example 2 in which (c) is not added. The same level.

[Industrial use possibility]

According to the polyurethane elastic yarn of the present invention, even when unsaturated fatty acid or heavy metal adheres to the yarn at the time of high temperature dyeing, superior heat resistance can be exhibited, and elasticity such as high elastic recovery and high elongation can be exhibited. The inherent superiority of the yarn is therefore particularly suitable for use in high temperature dyeing after being mixed with other fibers such as polyester or nylon fibers.

For example, it can be used for the use of the polyurethane elastic yarn of the present invention alone, and can also be used in combination with various fibers to obtain a superior stretch fabric, and can be knitted, woven, and taped. It is processed into a stretchable product.

The specific uses that can be used include socks, stockings, circular knits, tricots, swimwear, ski pants, overalls. , various types of fiber products, tight-fitting materials such as fire-fighting suits, golf pants, simple diving suits, bras, corsets, handbags, etc., and also include leak-proof materials for waterproofing products such as disposable diapers, tight materials for waterproof materials, and baits. , artificial flowers, electrical insulation materials, crepe cloth, copier descaler, liners, etc.

Claims (8)

A main constituent component comprising a high molecular weight urethane elastic yarn of a high molecular weight diol and a diisocyanate, wherein the polyurethane elastic yarn contains (a) a sterically hindered phenolic compound, and (b) N, N- a dialkylhalfcaquinone compound, and (c) a nitrogen-containing aromatic compound having a nitrogen-containing heteroaromatic ring having a nitrogen atom in an aromatic ring, and the content of the nitrogen-containing aromatic compound (c) is 0.01% by weight to 0.18 by weight %. The polyurethane elastic yarn of claim 1, wherein the nitrogen-containing aromatic compound (c) has a molecular weight of 300 or more. The polyurethane elastic yarn according to claim 1 or 2, wherein the nitrogen-containing aromatic compound (c) is an aromatic compound having two or more nitrogen atoms in the aromatic ring. Such as the polyurethane elastic yarn of claim 1 or 2, wherein the sterically hindered phenol compound (a) and the nitrogen-containing aromatic compound (c) are trinitrogen a compound. The polyurethane plastisel yarn of claim 4, wherein the sterically hindered phenol compound (a) is 1,3,5-paran (4-tertiary-butyl-3-hydroxy-2, 6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, and (c) the nitrogen-containing aromatic compound is 2,4-bis(2',4'-dimethylphenyl)-6-(2 "-Hydroxy-4"-alkoxyphenyl)-1,3,5-triazole . The polyurethane elastic yarn of claim 1 or 2, wherein the sterically hindered phenol compound (a) is a polymer derived from cresol. The polyurethane elastic yarn according to claim 1 or 2, wherein the content of the hindered phenol compound (a) is 0.1% by weight or more and 6.0% by weight. Hereinafter, the content of the N,N-dialkylhalfquinone compound (b) is 0.1% by weight or more and 6.0% by weight or less. A method for producing a polyurethane elastic yarn by adding (a) a sterically hindered phenol compound to a solution containing a polymer diol and a polyisocyanate of a main constituent component, (b) An N,N-dialkylcarbazone compound and (c) a nitrogen-containing aromatic compound having a nitrogen-containing heteroaromatic ring in which a nitrogen atom is disposed in an aromatic ring, and is contained in a polyurethane-containing compound The ratio of the nitrogen aromatic compound (c) is 0.01% by weight or more and 0.18% by weight or less of the polyurethane spinning solution, followed by spinning.